Synthetic and biosynthetic routes to nitrogen–nitrogen bonds

He, Haiyan; Niikura, Haruka; Du, Yi‐Ling; Ryan, Katherine S.

doi:10.1039/c7cs00458c

Cited by 63 publications

(65 citation statements)

References 285 publications

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“…It has been speculated that Gra originates from l -ornithine; therefore we also investigated whether 14 N-ornithine and 14 N-citrulline added to the P. graminis DSM 17151 growth medium with 15 NH 4 Cl are converted to Gra.…”

Section: Resultsmentioning

confidence: 99%

“…The origin and biosynthesis of the N–N bond in natural products have attracted much interest, , in part due to the anticancer drug streptozocin (Zanosar, Figure ) isolated from Streptomyces achromogenes var. streptozoticus NRRL 2697, which is effective against pancreatic cancers. , The enzyme SznF in the biosynthetic gene cluster (BGC) of streptozocin is reported to catalyze the formation of the N- nitrosourea group (Figure ).…”

Section: Introductionmentioning

confidence: 99%

“…In contrast to NONOates, which have yet to be identified in natural products, little is known about the reactivity of C-type diazeniumdiolate natural products and the conditions under which NO may be released (Figure 1). 8,16 The origin and biosynthesis of the N−N bond in natural products have attracted much interest, 1,17 in part due to the anticancer drug streptozocin (Zanosar, Figure 1) isolated from Streptomyces achromogenes var. streptozoticus NRRL 2697, which is effective against pancreatic cancers.…”

Section: ■ Introductionmentioning

confidence: 99%

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C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

et al. 2022

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Siderophores are synthesized by microbes to facilitate iron acquisition required for growth. Catecholate, hydroxamate, and α-hydroxycarboxylate groups comprise well-established ligands coordinating Fe(III) in siderophores. Recently, a C-type diazeniumdiolate ligand in the newly identified amino acid graminine (Gra) was found in the siderophore gramibactin (Gbt) produced by Paraburkholderia graminis DSM 17151. The N−N bond in the diazeniumdiolate is a distinguishing feature of Gra, yet the origin and reactivity of this C-type diazeniumdiolate group has remained elusive until now. Here, we identify L-arginine as the direct precursor to L-Gra through the isotopic labeling of L-Arg, L-ornithine, and L-citrulline. Furthermore, these isotopic labeling studies establish that the N−N bond in Gra must be formed between the N δ and N ω of the guanidinium group in L-Arg. We also show the diazeniumdiolate groups in apo-Gbt are photoreactive, with loss of nitric oxide (NO) and H + from each D-Gra yielding E/Z oxime isomers in the photoproduct. With the loss of Gbt's ability to chelate Fe(III) upon exposure to UV light, our results hint at this siderophore playing a larger ecological role. Not only are NO and oximes important in plant biology for communication and defense, but so too are NO-releasing compounds and oximes attractive in medicinal applications. Articles pubs.acs.org/acschemicalbiology

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

et al. 2022

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“…[2][3][4] However, the mechanisms of NÀ N bond biosynthesis were not understood until recently. [5][6][7] The diazo group is an important functional group with an NÀ N bond. It has been used in organic chemistry for a long time because it is highly reactive and can be used as a precursor for various scaffolds by chemical modification.…”

Section: Introductionmentioning

confidence: 99%

Bacterial Avenalumic Acid Biosynthesis Includes Substitution of an Aromatic Amino Group for Hydride by Nitrous Acid Dependent Diazotization

et al. 2022

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The diazo group is an important functional group that can confer biological activity to natural products owing to its high reactivity. Recent studies have revealed that diazo groups are synthesized from amino groups using nitrous acid in secondary metabolites of actinomycetes. However, genome database analysis indicated that there are still many diazo group‐biosynthesizing enzymes for unknown biosynthetic pathways. Here, we discovered an avenalumic acid biosynthesis gene cluster in Streptomyces sp. RI‐77 by genome mining of enzymes involved in diazo group formation. Through heterologous expression, the gene cluster was revealed to direct avenalumic acid (AVA) biosynthesis via 3‐aminoavenalumic acid (3‐AAA). In vitro enzyme assays showed that AvaA6 and AvaA7 catalyzed the diazotization of 3‐AAA using nitrous acid and substitution of the diazo group for hydride to synthesize AVA, respectively. This study revealed an unprecedented pathway for amino group removal via diazotization.

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“…[35][36] Aromatic nitroso compounds are active intermediates in C-N and N-N bond synthesis. [37][38][39][40][41][42] During C-N bond formation, aromatic nitroso groups often serve as electrophiles; 34…”

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confidence: 99%

Chemoenzymatic Cascade Synthesis of Phenol Diarylamine Using Non-Heme Diiron N-Oxygenase

Guo

Tian

Wang

et al. 2022

Preprint

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Diarylamines are important moieties in organic materials and bioactive molecules. The traditional synthetic approach to diarylamines is metal catalysis in organic solvents. Herein, we report the chemoenzymatic cascade synthesis of phenol diarylamines. Non-heme diiron N-oxygenase AzoC, which catalyzes the oxidization of amines to nitroso groups for azoxymycins biosynthesis in Streptomyces chattanoogensis, is engineered as a catalyst. This synthetic method bears a broad range of phenol and aniline substrates. Mechanistic study indicates that the enzymatically formed nitroso intermediate couple to phenoxide facilitates the non-enzymatic diarylamine synthesis. Our study suggests that diarylamines can be enzymatic synthesized in aqueous solutions and highlights the synthetic potential of non-heme diiron N-oxygenases.

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Synthetic and biosynthetic routes to nitrogen–nitrogen bonds

Abstract: The nitrogen–nitrogen bond is a core feature of diverse functional groups like hydrazines, nitrosamines, diazos, and pyrazoles.

Cited by 63 publications

References 285 publications

C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

Bacterial Avenalumic Acid Biosynthesis Includes Substitution of an Aromatic Amino Group for Hydride by Nitrous Acid Dependent Diazotization

Chemoenzymatic Cascade Synthesis of Phenol Diarylamine Using Non-Heme Diiron N-Oxygenase

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Synthetic and biosynthetic routes to nitrogen–nitrogen bonds

Abstract: The nitrogen–nitrogen bond is a core feature of diverse functional groups like hydrazines, nitrosamines, diazos, and pyrazoles.

Cited by 63 publications

References 285 publications

C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

C-Diazeniumdiolate Graminine in the Siderophore Gramibactin Is Photoreactive and Originates from Arginine

Bacterial Avenalumic Acid Biosynthesis Includes Substitution of an Aromatic Amino Group for Hydride by Nitrous Acid Dependent Diazotization

﻿Chemoenzymatic Cascade Synthesis of Phenol Diarylamine Using Non-Heme Diiron N-Oxygenase

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Chemoenzymatic Cascade Synthesis of Phenol Diarylamine Using Non-Heme Diiron N-Oxygenase